Production of colored photographic pictures



Patented Oct. 29, 1946 PRODUCTION OF COLORED PHOTOGRAPH) PICTURES Bla Gaspar, Hollywood, Calif., assignor to Chromogen, Incorporated, a corporation of Nevada No Drawing. Continuation of application Serial No. 412,341, September 25, 1941, which is a division of application Serial No. 179,591, December 13, 1937. This application February 7, 1944, Serial No. 521,439.

cember 14, 1936 24 Claims.

In Great Britain De- 2 Quinoxaline of the following formula:

1 This application is a continuation of my appli- 1 cation Serial No. 412,341, filed September 25, 1941, which is a division of application Serial No. 179,- 591, filed December 13, 1937, now Reissue Patent 22,308.

In my earlier patents a process has been described for the production of dyestuff images from diffusely dyed silver images. Thus, for example, according to my United States Letters Patent No. 2,020,775, dated November 12, 1935, the production of such dyestufi images is performed by treating the diffusely dyed silver image with solutions which destroy the dye locally in the presence of the metal deposit of the photographic image. At the same time the silver is partially or totally converted into a silver compound. Individual cases, in which the destruction of the dye can be accelerated by the addition of certain substances, have been described in my. abovementioned patent. a i

It has been found that the effectiveness of the. dye-destroying solutions described in my United StatesLetters Patent No. 2,020,775 and of the other dye-destroying baths which were found to beapplicable in the process can be accelerated j by a great number of substances other than those heretofore known. A large number of the. substances added in accordance with this invention enable the treating solutions to work in a much" more eiiective manner, e. g., in a much shortertime or in far smaller concentration, than the products previously proposed as accelerators.

N Diphenyl-quinoxaline of the following formula:

or similar compounds of the general formula:

of which the formula:

' is a more specific example. In this formula X and Y represent groups like nitrogen, sulfur, oxygen, ,carbonyle C,=0, carbimino C=NI-ll, and the ino-groups, oxy groups, alkyl-groups,

Inview of the great effectiveness of the addi- I tions, much smaller amounts of these accelerating substances are sufficient. .In many cases the.

presence of the accelerating compounds in the ratio of 1:i00,000 is sufficient to multiply the effectiveness of the dye-destroying solution.

As substances which I have found to be strong accelerators, the following may be mentioned:

2,3-di-amino-phenazine of thef ollowing for mula:

N O UNI}: NH: \N

2-oXy-3-amino-phenazine of the following for- Inula:

like. The compounds may be substituted by ammy]- groups, or othersubstituents including also sulionic-groups.

Example 1 A 1% aqueous solution of hydrochloric acid which alone will not work satisfactorily on a layer diffusely colored by Diamine Fast Pink G (a dyestufl furnished ,by the I. G. Farbenindustrie Akt. Ges.).may be activated by the addition of 0.002%

-of 2,3-diamino-phenazine.

Example 2 Theaction of a 2 /2% aqueous solution of hydrobromic acid on the dyestufi Heliotrope B (Schultz Farbstofitabellen, 1931, 7th edition, vol..

, 1,' No. 494) may be considerably accelerated by the addition of 0.002% of diamino-phenazine. Even the addition oi 7 parts of diamino-phenazine to one mill-ion parts of a hydrobromic acid solution of 1.66% strength has a distinct accelcrating reats the local destruction of HeliotropeB. V

Example 3 For the production of multicolor images a multi-layenmaterial.maybe used having different dyestuffs incorporated-in layers in which different color; selection. pictures are recorded. The

3 V dyestuffsflmay be forexample Diamine Pure Blue FF (Schultz loo. cit: ;No. 510), 3361 20Light-'if e1- low 4 GL'extra (Schultz 10c. cit. No. 308) and Sirius Ruby 13 (furnished by the I. G. Farbeninchosen for the tests are in most case insoluble azodyestufis which in themselves are difficult to bleach out. In usingdyestuifs of this sort, the difierences are naturally more evident than if dustrie Akt. Ges). The dye-destroying solution 5 dyestufis are employed wihch are bleached out consists of 4% aqueous solution ,f -hydr0b romic in a shorter time-in a dyestuff destroying bath acid which has been activated by the addition of without admixture. In using insoluble dye- 0.002% of diamino-phenazine. stuffs which are difiicultly bleached, the difierence tisisdgreat'that, for instance, the thio-carbamide Example l0 bath mentioned'in Example 4 which with an ad- A solution containing 70 g. thiocarbamide, 39 mixture of, for instance, 2,3-diamino-phenaz1ne hydroquinone, 50 chrome alum ccmlsulfur'ic destroys the .dyestufisjlocaily after 7 or 8 minutes acid (d:1 85) per liter, t e f dd 'b of treatment shows practically no useful effect if g. 2,3-diamino-phenazine is used for tr ti .g, the accelerating substance is omitted, even if the posed and developed silver halide layers containm- 'f;treatmenti1s doubled' ing the dyestufi obtained from diazotised ortho- Men-non 1 1 however made of the faict anisidine and resorcinoL A dyestufi image is that the application of the admixtures has certain tamed after seven minutesrtreating advantages even in the case of easily soluble and easily bleaching dyestuff, such as a shortening of 7 E a ple .5 20 the time of treatment and thereby a decreaseof A solution containing 74 g. potassium bromide gfi i g i i f d and 17% com. sulfuric acid '(d=1.84) per liter'is fi g i g s saturated with 2,3-diphenyl-quinoxaline and then W es n foun t u f? contains less than 0.01 g. per liter of this subcelerators are giver} m the i 11st Whlch stance. The solution acts on silver images dyed 25 h-Q the'accglera'tmg effect 'obtamed by t with the 'dyestuff obtained from diazotised 4- of Vamus *i to a number amino-l-benzoylamino 3-methoxy-6-methylbentreatlrig baths used mprodutcmig'dyestufi images Z01 and flmaphtd Within 25 minutes or on fromsilver magesdyedby six different dyestufis. the dyestuff obtained from diazotised o-ani- TheSedyestufi-s are: sidine and resorcinol Within 30 minutes or 30 A.Pontamine Sky Blue :6 B (Schultz loc. cit. No. on the dyestuff obtained from diazotised p- 5 10:); nitraniline and fl-naphtol within 60 minutes. B. Chlorantine'Light Green BB Cibar With this dyestufi and with the same treating C. Tu-checht Brillantrot2jB Ci ba. bath the same result is obtained if, instead of D. Benzolight Red 8 :BL (Schultz loc. cit. No. the 2,3-diphenyl-quinoxaline, the 2,3-dimethyl- 35 .566). quinoxaline, the 2-oxy-3-methylquinoxa1ine or :Congo-SkyBlue (Schultzloc. cit.No. 513). ordinary quinoxaline are used, ,2 g. of each ac- F. :Chlorantine Fast Orange TRL (Schultz loo. celerato'r being used per liter. The dyestufis cit. :No. 706-).

Accelerati eflect. D t ft No Catalyst I hydrochlo acid 1%, 13:3

., Lg V ,1 Benzhydrol" i c A, B, o. 2 Alphabenzil-dioxime .s A,'B,C. 3 Benzophen ne-anil A,B. 4' Cyanamide... Ci 5 Diacetyl-monomethnxime A,.B,C.' 6}; Diacetyl-monoxime A,lB. 7:, Dibenzylamine A, B. 8 Diphenyl-piperazine A,B. '9; Diphenyl-thiocarbazona A, B. 10 Hydrobenzamide A,B,C. l1 Methylene-amino acetonitrileJ A,B. 12 .Quinizarine..- 11,13. 13' Quinophtalone. B. 1 1 2,2,4,4-tetramino-5,5-dimethyl-diphenylmethane A,'B. 1 Tetra-ethyl-p-diamino-benzophenone A,B. 16 Tetra-ethybpp diamino-dipheny1-methane. A,B. 17 Benzothio-diazo L v A,B,C. 18 2,3 dimethyl-quinoxaline. A, B. 2,3 diamino-phenazine, A, 13,0. 20 2-oxy-3-amino-phenazine. 'A,'B,C. 21 N,N-di(paraamino-phenyl) ----r A,'B. 22 Methyl-violettB A,,B,C. 23 Aummine A,B. 24 Diacetyl-p-phenylene-diamine. A, 13,,(3. 25 S-diphenylethylene-diaminen A,B. 26 2,4-diaminodiphenylamine. A,B. 7 Quinizarine sulphonic acid ,A,.B. 8 Sodium indigo sulphom A,B. 29 1,2,4-triaminobenzene-trihydrochloride A,B. 30 Tetramethyl-diamino-benzhydr01. A,B,C. 31- TetramethyLp-diamino-benzophenone A, 13,0. 32 Tetramethyl-p-phenylene-diamine-hydrochloride.i A, B,C. '33 Tetramethyl-p-diamino-diphenyl methane I A, B. r .4 1N-,methyl-fquinolone Hydrobrloiile acid 5% A, B. 35 Hydrochrfiiacid 11% A,B. :36 Acetone-phenylhydrazone A,B. '37 Acetone-oxime C.- 38 Acridone A,'B. 39 fi-amino-purine sul A,B. I .40- Amino-pyrine A,B,C. 41 Allantoin -J+ A,B,C. $2 ,Anthraquinqne-betasul ho A,B. 43 Benzalmethylamine v A,B,C. 44 1Diacetyl-o-phenylendiamine A,B. 45 jiBenzthiazylhxdrazine. A,B. :1 e lp fifi di mln z nm 47 Gym. 'phe yl-carbazide A,B. 48 Anfhrsmuinnna R A,B,C.

Accelerating cflect on Dyestufl Catalyst. hydrochloric acid 11% used 49 2,3-diphenyl-quinoxaline; l. A, B. 50 l,am no-anthmquinone.. A, B. 51 2,ammo-anthraquinone A,B.

., 53 Lmethyl-Z-pyridona. A, B, O 54 Alizarine-redS A, B. 55 Alizarine-red-agfa A, B. 56 Dibydro-Z-hydrox A, B. 57 Fuchsine A.

58 Anthraquinone-beta-sulphonic acid Sogdflium hyposulphite D.

59 'letramethyl-p-diarnmo benzophenone Accelerating effect on D; I v llilydrochloric acid 60 Qumizanne sulphonic acid Sodium chloride 20% .E. plus hydrochloric 61 do Magnesium chloride F.

. i 20% plus hydro- A chloric acid.

i 62 Dlrnethylammostyryl dunethyl-thiazol-N-methyhodide Hydrochlo{r 1 ac1dll%. A, B. 63 6,methoXy-pseudocyanine N-ethyl-iodide A, B.

, 64 N-ethyl-6,methoxy-thiocarbocyanine-iodide A,B. 65 N ethyl-benzthioazol-carbocyanine-iodide. A, B. 66 Quinone 1 r 67 Benzalaniline C.

68 Hexamethylenetetra A, B. 69 Benzalazine A, B. 70 p-Toluol-sulphinic acid O. 71 Benzene-l-sulphonic fi-sulphinic acid.

72 Naphtalene-l-sulphonic 4-sulphinic acid O.

i '73 (3)nitrostyryl-quinolinium-Nethyl-ethylsulphonate- A, B. 74 g3)nitrostyryl-benz-thiazol-ethyl-sulphonate A, B.

75 3)sulpho-styryl-pseudo-thiohydantoine A, B.

. 76 Styrylequinolinium-ethyl-sulphonate. A, B.

77 .(4)dimethylamino-styryl-rhodanine A, B. 78 Bis (4-dimethylamino-2-nitro-phenyl) disulphide A, B.

Q'I'he foregoing list of accelerating compounds embodies the results obtained with catalysts belonging to various classes of compounds. It includes, for example, substances of the general type disclosed in my earlier Patent No. 2,020,775, dated November.12,1935. In addition, the list includes compounds of the class of reducible organic'substances, the reduction products of which are re-oxidizable during the treatment of a dyed silver image to the original reducible substance which are claimed in application Serial No. 179,591, now Reissue Patent 22,308. The claims of the present application are directed to dye destruction baths and processes employing diphenylmethane and triphenyl-methane derivatives although the general listing of compounds have been set forth to indicate the comparative activity of the various accelerating compounds.

The quantity of the added catalyst was 0.2% in the experiments Nos. 1 to 57 and 60 to 69 of the list, 0.8% was used'in No. 58 and 0.5% was used in No. 59. In Nos. 70' to 72, 1% of the addition was used; In Nos. 73 to '77 the quantity of the addition was again 0.05%. In many'cases far smaller quantities of the catalystmay be used for practical purposes.

As can be seen, the new catalysts belong to diiferent chemical groups. They are in most cases organic substances which can be easily hydrated or dehydrated. Compounds, the reduction products or oxidation products of which are capable offorming areversible redox-system, are especially suitable. See, for example, Nos. 26, 33, 57. Furthermore, organic bases which can be easily oxidizedmay be used, See Nos. 29, 32, 44. .In many cases. the bases themselves are not especially effective but can be rendered more suitable by the formation of oxidation products by autoxidation. The oxidation products of such bases are very suitable catalysts. Heterocyclic bases can also beused. See Nos. 17, 8. In many casesthecompounds which are found to be suitable catalysts are characterized by the presence of a CO group or :03 group, these groups being present in a carbocyclic or heterocyclic nucleus. See No. 53. If the =00 group appears several times in such a compound as is the case in quinone or *quinone derivatives the effectiveness ,"iS especially good. 1 See Nos. 48, 50, 51, 52, 58, 42, 66'. Aliphatic compounds with-=COgroups or :08 groups are also suitable in many cases. See Nos. 15,. 31. Hereagain several of such groups maybe present in the molecule. In other cases the effective compounds are characterized by the presence of the group =C=N, either in a ring system (No. 39) or in an open chain... See Nos. 2, 3, 5, 6, 11, 36, 37, 43. Compounds of the quinone-imide type or indophenols belong to this group of catalysts. Also the compounds containingthe C=N group show in many cases an accelerating effect. A large class of accelerators is found in the class of sensitizing or desensitizing dyestuffs. See,for example, Nos. 62, 63, 64, .73to 77. The capacity of accelerating appears to bein no direct proportion to the sensitizing properties but on the contrary to be based mainly on the fact that these dyestuifs usually belong to one of the above-mentioned groups of accelerating substances. It may be noted that organic sulphocompounds, compounds containing -SS-; -S.- H or SOzH groups are also suitable accelerators. The soluble derivatives of vat dyes are found to be also efiective as catalysts. The tests described in the'above given list of results are only examples of suitable catalysts and dyes and may :be regarded as an illustration only, of the new -process without restriction to the dyes, catalysts or treatingsolutions used in the ex,- amples. v 1 f WhatIclaimisL 1. In a process of producing a photographic dyestufi image in a photographic emulsionuniformly dyed by an azo-dye and also comprising a metal image, the step of treating said nietal image with a solution containing an agent which is nondestructive With respect to. the .dyestufi, but which reacts with the said metal to oxidize it and substantially simultaneously to form a reducing substance which destroys said azodye at the points of the metal image, said ,solution further containing a small amount of a diphenylmethane derivative which is reducible and the reduction products thereof are reoxidlzable during the treatment of the metal image to the original diphenylmethane derivative.

2. In a process of producing a photographic dyestuff image from a silver image uniformly dyed by an azo-dye, the step of treating said silver image with a solution containing a substance capable of selectively destroying said .azo-Idye by reduction in the presence of a photographic silver image and comprising a small amount of a reducible diphenylmethane derivative, the .reduction products of which are re-oxidizable during the treatment of said silver'image with said solution to the original reducible diphenylmethane derivative.

3. In a process of producing a photographic dyestuif image in a photographic emulsion uniformly dyed by an a-Zo-dye and also comprising a silver image, the step of treating said silver image with a solution containin an agent capable of forming complex silver :compo-unds and which acts to selectively destroy said azo-dye by reduction in the presence of said silver image and a small amount of diphenylmethane derivative which is reducible and the reduction products thereof are re-oXidizab-le during the treatment of the silver image to the original diphenylmethane derivative. v. 4. In a process of producing a photographic dyestuff image from a silver image uniformly dyed byan azo-dye, the step of treating said silver image Witha solution comprising hydrohalic acid and a small amount of a diphenylmethane derivative which is reducible and the reduction -prod-, ucts thereof are re-oxidizable during the production of said dyestuiT image to the original diphenylmethane derivative. 1 I 5. In a process of producing a photographic dyestu-if image from a silver image uniformly dyed by an azo-dye, the step of treating said sil ver image with a solution comprising thiocarbamide and a small amount of a diphenylmethane derivative which is reducible and the reduction products thereof are re-oxidizable during 'the production of said dyestuff image to the original diphenylmethane derivative.

6. In a process of producing a photographic dyestuif image from a silver image uniformly I dyed by an azo-dye, the step of treating said silver image with a solution comprising hydrochloric acid and a small amount of a diphenylmethane derivative which is reducible and the reduction products thereof are re-oxidizable during the production of said dyestufi image to the original diphenylmethane derivative.

I "7. Atreating bath for producing a photographic .dyestuff image in a photographic emulsion uni- -'forml y dyed by an azo-dye and also comprising aisilver image, comprising a substance which is non-destructive with respect to the dyestuff, but "reacts with the silver to oxidize it and substantially simultaneously to form .a reducing @substance which destroys said azo-djye at the points Qt phe sijlv'er image and also comprising a-small amount of a diphenylmethane derivative which is reducible'during the production of the dyestuff l a wn. I'"

8.,A treating bath for producing a photographic,

phenylmethane derivative which is reducible during the production of said dyestuifimage.

9. A treating bath for producing a photographic dyestuff image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising a substance capable-of iforming complex silver compounds and which acts to selectively destroy said azo-dye by reduction in the presence of said silver image and a small amount of a. diphenylmethane derivative which is reducible during the production of said dyestuif image.

10. A treating bath for producing a photographic dyestuff image in a photographic emulsion uniformlydyed by anazo-dye and also comprising a silver image, comprising hydrohalic acid and a small amount of a diphenylmethane derivative which is reducible during the production of said dyestufi. image.

11. A treating bath for producing a photographic dyestuff image in a photographicemulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising thiocarbamide and a small amount of a diphenylmethane derivative which is reducible :during the production of said dyestuif image.

- 12, A treating bath for producing ,aphotographic dyestufiimage in a photographic emulsion uniformly .dyed with an .azo-dye and .also comprising a silver, image, comprising hydrochloric acid and a small amount of .a diphenylmethane derivative which is reducible during the production of the said dyestufi image.

13; .In a process of producing .a dyestuff image in a, photographic emulsion comprising a silver image andia uniformly distributed azo-dyestu fl, the stepof treating said azo-dyestuff mule presence of said silver image with thio-car-bamide, said treatment being carried out in .the presence of a small amount of a diphenylmethane derivative which is reducible and the reduction products thereof are re-oxidizable during the production of said dyestufi image to the original diphenylmethane derivative.

14. In a process of producing a dyestufi image in 'a photographic emulsion comprising a silver image and a uniformly distributed azo-dyestuff, the step of treating said azo-dyestuff'in the presence of said silver image with hydrohalic acid, said treatment being carried out in the presence of a small amount of a diphenylmethane derivative which is reducible and the reduction products thereof are re-oxidizable during the production of said dyestuff imageto the original diphenylmethane derivative.

15. 'In a process of producing a dyestuif image in a photographic emulsion comprising a silver image and a uniformly distributed azo dyestuff, the step of treating said azo-dyestufi in the presence of said silver image-with hydrochloric acid, said treatment being carried out in the presence of a small amount of adiphenylmethane derivative which is reducible and the reduction products thereof are re-oxidizable during the production :Of said dyestuif image to the original diphenyl methane derivative." i f "16.' A treating bath ;for producing apnea; graphic dyestuff image in a photographic emul sion uniformly dyed by an azo-dye and also comprising a silver image, comprising a substance capable of selectively destroying said azo-dye by reduction in the presence of said silver image, said bath also comprising a small amount of an organic compound soluble therein and capable of accelerating the selective dye destructive action of said substance, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

1'7. A treating bath for producing a photographic dyestuff image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising hydrohalic acid and a small amount of an organic compound soluble in said bath and capable of accelerating the selective dye destructive action of said hydrohalic acid, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

18. A treating bath for producing a photographic dyestuff image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising thiocarbamide and a small amount of an organic compound solubl in said bath and capable of accelerating the selective dye destructive action of said thiocarbamide, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

19. A treating bath for producing a photographic dyestuff image in a photographic emulsion uniformly dyed by an azo-dye and also comprising a silver image, comprising hydrochloric acid and a small amount of an organic compound soluble in said bath and capable of accelerating the selective dye destructive action of said hydrochloric acid, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

20. In a process of producing a dyestuff image from a silver image and a uniformly distributed azo-dyestuff in a photographic emulsion, the step of treating said azo-dyestuff in the presence of said silver image with a substance capable of selectively destroying said azo-dyestuif by reduction in the presence of a photographic silver image, said treatment being carried out in the presence of a small amount of an organic compound capable of accelerating the selective dye destructive action of said substance, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

21. In a process of producing a dyestuff image from a silver image and a uniformly distributed azo-dyestuif in a photographic emulsion, the step of treating said azo-dyestuff in the presence of said silver image with thio-carbamide, said treatment being carried out in the presence of a small amount of an organic compound capable of accelerating the selective dye destructive action of said thiocarbamide, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

22. In a process of producing a dyestuif image from a silver image and a uniformly distributed azo-dyestuff in a photographic emulsion, the step of treating said azo-dyestufi in the presence of said silver image with hydrohalic acid, said treatment being carried out in the presence of a small amount of an organic compound capable of accelerating the selective dye destructive action of said hydrohalic acid, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

23. In a process of producing a dyestufi image from a silver image and a uniformly distributed azo-dyestuff in a photographic emulsion, the step of treating said azo-dyestufi in the presence of said silver image with hydrochloric acid, said treatment being carried out in the presence of a small amount of an organic compound capable of accelerating the selective dye destructive action of said hydrochloric acid, said compound being selected from the group consisting of diphenylmethane derivatives and triphenylmethane derivatives.

24. In a process of producing a dyestuff image in a photographic emulsion comprising a silver image and a uniformly distributed azo-dyestufi', the step of treating said azo-dyestufi in the presence of said silver image with a substance capable of selectively destroying said azo-dyestuff by reduction in the presence of a photographic silver image, said treatment being carried out in the presence of a small amount of a diphenylmethane derivative which is reducible and the reduction products thereof are re-oxidizable during the production of said dyestuff image to the original diphenylmethane derivative.

- BELA GAsPAR. 

